EP2698354B1 - Procédé de dégazage sous vide de verre fondu, procédé de fabrication de verre fondu, procédé de fabrication d'un article constitué de verre - Google Patents

Procédé de dégazage sous vide de verre fondu, procédé de fabrication de verre fondu, procédé de fabrication d'un article constitué de verre Download PDF

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Publication number
EP2698354B1
EP2698354B1 EP12770966.5A EP12770966A EP2698354B1 EP 2698354 B1 EP2698354 B1 EP 2698354B1 EP 12770966 A EP12770966 A EP 12770966A EP 2698354 B1 EP2698354 B1 EP 2698354B1
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Prior art keywords
glass
molten glass
vacuum
vacuum degassing
degassing
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EP12770966.5A
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German (de)
English (en)
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EP2698354A4 (fr
EP2698354A1 (fr
Inventor
Terutaka Maehara
Rei Kitamura
Shuji Kabashima
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AGC Inc
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Asahi Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/225—Refining
    • C03B5/2252—Refining under reduced pressure, e.g. with vacuum refiners
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/225—Refining

Definitions

  • the present invention relates to a method for vacuum-degassing molten glass, a process for producing molten glass, and a process for producing a glass product.
  • a refining step of removing bubbles formed in molten glass is carried out prior to forming in a forming apparatus of molten glass formed by melting glass materials in a melting tank.
  • a method has been known wherein a refining agent such as sodium sulfate (Na 2 SO 4 ) is preliminarily blended with the materials, and molten glass obtained by melting the materials is stored and held at a predetermined temperature for a certain time, whereby bubbles in the molten glass are made to grow and float up by the refining agent and are removed.
  • a refining agent such as sodium sulfate (Na 2 SO 4 ) is preliminarily blended with the materials, and molten glass obtained by melting the materials is stored and held at a predetermined temperature for a certain time, whereby bubbles in the molten glass are made to grow and float up by the refining agent and are removed.
  • a vacuum degassing method wherein molten glass is passed through a vacuum degassing vessel, the interior of which is maintained in a predetermined degree of vacuum, whereby bubbles included in the molten glass are made to grow in a relatively short time, and the bubbles are made to float up to the surface of the molten glass employing buoyancy of the grown bubbles, and the bubbles are broken at the surface of the molten glass, whereby the bubbles are removed from the molten glass.
  • the present applicant has disclosed that the bubbles in the molten glass can effectively be removed by adjusting the pressure in the vacuum degassing vessel to be lower than the bubble growth starting pressure determined by the moisture concentration ( ⁇ -OH value) in the glass, the SO 3 concentration and the temperature of the molten glass (Patent Document 1).
  • Patent Document 2 discloses that formation of bubbles can be suppressed by defining the content of SO 3 in the molten glass within a predetermined range.
  • JP 2006 298657 A discloses a vacuum defoaming apparatus of molten glass provided with: a vacuum housing to be sucked in vacuum; the vacuum defoaming tank arranged in the vacuum housing for defoaming molten glass under vacuum; an introduction means arranged to be communicated with the vacuum defoaming tank for introducing the molten glass to be defoamed under vacuum into the vacuum defoaming tank; a discharge means arranged to be communicated with the vacuum defoaming tank for discharging the vacuum-defoamed molten glass from the vacuum defoaming tank; and a mechanism for inclining a glass flow passage in the vacuum defoaming tank with respect to the horizontal direction, namely, raising the upstream side of the vacuum defoaming tank or lowering the downstream side of the defoaming tank.
  • EP 2 272 806 A1 describes vacuum defoaming equipment, equipment for producing a glass product, and a method for producing a glass product.
  • Patent Document 2 discloses the bubbles, it failed to disclose the relation between the bubbles and the vacuum-degassing step.
  • the object of the present invention is to provide a vacuum-degassing method, with which reboiling can be suppressed.
  • the object of the present invention is to provide a process for producing molten glass and a process for producing a glass product, employing the above vacuum-degassing method.
  • reboiling and “reboil bubbles” are not specified by the causes and the location where they occur, specifically, whether they occur in the molten glass or at the interface between the molten glass and the furnace material. However, the wordings here mean the above-described narrowly-defined wordings limited to bubbles in the vacuum degassing vessel.
  • the present inventors have conducted extensive studies on a vacuum-degassing method capable of suppressing formation of new bubbles by reboiling while effectively removing the bubbles in the molten glass.
  • pS O 2 K ′ ⁇ S O 3 p O 2
  • the silicate glass has a composition of SiO 2 ⁇ 50 mol% and (alkali component oxide plus alkaline earth component oxide) ⁇ 10 mol%.
  • the alkali component oxide means Li 2 O, Na 2 O and K 2 O.
  • the alkaline earth component oxide means MgO, CaO, BaO and SrO.
  • the present invention provides a process for producing molten glass, which comprises a step of degassing molten glass by the above method for vacuum-degassing molten glass, and a melting step of melting glass materials prior to the degassing step.
  • the present invention provides a process for producing a glass product, which comprises a step of producing molten glass by the above process for producing molten glass, a forming step of forming the molten glass downstream the step for producing molten glass, and an annealing step of annealing the glass after formed.
  • the method for vacuum-degassing molten glass of the present invention by carrying out vacuum-degassing under conditions satisfying the above formula (1), reboiling in the vicinity of the bottom portion of the vacuum degassing vessel by excessive pressure reduction can be suppressed. Therefore, the reboil bubbles will not remain in the molten glass, and the quality of the molten glass and a glass product to be produced can be improved.
  • an excellent vacuum degassing effect can be realized by employing the above-described vacuum-degassing method.
  • a high quality glass product can be provided by employing the above-described process for producing molten glass.
  • Fig. 1 is a cross sectional view schematically illustrating a general apparatus for vacuum-degassing molten glass to be employed for the vacuum-degassing method of the present invention.
  • a vacuum degassing apparatus 100 shown in Fig. 1 is used in a process for vacuum-degassing molten glass G supplied from a melting tank 1 and continuously supplying the degassed molten glass to a forming apparatus 200 in a subsequent step.
  • the vacuum degassing apparatus 100 includes a vacuum housing 2 made of a metal such as stainless steel, the interior of which can be maintained in a reduced pressure state at a time of operation.
  • the vacuum housing 2 has a vacuum degassing vessel 3 accommodated therein so that its long axis is in parallel with the horizontal direction.
  • This vacuum degassing vessel 3 is a vessel in the form of an oblong box shape comprising a bottom wall 3a, side walls 3b and a ceiling wall 3c.
  • the vacuum degassing vessel 3 is designed so that the air pressure in it is less than the atmospheric pressure, and makes bubbles in the supplied molten glass G to float up and be broken.
  • an uprising pipe 5 as a supply mechanism is connected via an introduction port 3d so as to vertically extend, and to a lower face of the other end side, a downfalling pipe 6 as a sending mechanism is connected via an exit port 3e so as to vertically extend.
  • the uprising pipe 5 and the downfalling pipe 6 are disposed so as to communicate with outside through an introduction port 2a and an exit port 2b formed on the bottom side of the vacuum housing 2, respectively.
  • each of the vacuum degassing vessel 3, the uprising pipe 5 and the downfalling pipe 6 has a structure consisting of a hollow tube made of a ceramic non-metallic inorganic material, or made of platinum or a platinum alloy, which are excellent in the heat resistance and the corrosion resistance to the molten glass, or a combination thereof.
  • the vacuum degassing vessel 3 is made of a ceramic non-metallic inorganic material
  • the vacuum degassing vessel 3 is preferably such that its outer shape has a rectangular cross section, it is made of heat-insulating bricks, and the shape of its interior constituting the flow passage for the molten glass has a rectangular cross section.
  • the shape of the interior of the vacuum degassing vessel 3 constituting the flow passage for the molten glass preferably has a circular or elliptic cross section.
  • the uprising pipe 5 and the downfalling pipe 6, in addition to platinum or a platinum alloy, reinforced platinum having a metal oxide dispersed in platinum or a platinum alloy may be mentioned.
  • the metal oxide to be dispersed may be a metal oxide of the Group 3, 4 or 13 of the Long Periodic Table, represented by Al 2 O 3 , ZrO 2 or Y 2 O 3 .
  • the ceramic non-metallic inorganic material may be dense refractories. Further, dense refractories lined with platinum or a platinum alloy may also be used.
  • the vacuum degassing vessel 3 is preferably constituted by heat-insulating bricks such as electrocast bricks.
  • the downfalling pipe 6 sends the molten glass G after vacuum-degassed to the subsequent treatment vessel (not shown). Accordingly, a lower end 6a of the downfalling pipe 6 is inserted into an open end of a downstream pit 13 and immersed in the molten glass G in the downstream pit 13. Further, a forming apparatus 200 is connected to the downstream side of the downstream pit 13.
  • the uprising pipe 5 constitutes a supply mechanism to supply the molten glass to the vacuum degassing vessel
  • the downfalling pipe 6 constitutes a molten glass sending mechanism to send the molten glass after degassed in the vacuum degassing vessel to the subsequent step.
  • upstream and downstream respectively mean an upstream side and a downstream side in the flowing direction of the molten glass G flowing through the glass flow passage 3R of the vacuum degassing apparatus 100.
  • the molten glass G supplied from the melting tank 1 is passed through the glass flow passage 3R in the vacuum degassing vessel 3, the interior of which is depressurized to a predetermined degree of vacuum to carry out vacuum-degassing.
  • the molten glass G is preferably continuously supplied to the vacuum degassing vessel 3 and continuously discharged from the vacuum degassing vessel 3.
  • the molten glass G to be used in the vacuum degassing method of the present invention is one formed by melting glass materials to be silicate glass.
  • the silicate glass preferably contains at least 50 mol% of SiO 2 with a view to obtaining the chemical durability endurable for practical use, more preferably at least 60 mol% with a view to further improving the chemical durability, further preferably at least 65 mol% with a view to still further improving the chemical durability.
  • the total content of an alkali component oxide and an alkaline earth component oxide is preferably at least 10 mol% with a view to suppressing phase separation of the molten glass, more preferably at least 15 mol% with a view to lowering the viscosity of the molten glass to lower the working temperature in each step, further preferably at least 20 mol% with a view to further lowering the viscosity of the molten glass to lower the working temperature in each step.
  • the alkali component oxide means Li 2 O, Na 2 O and K 2 O.
  • the alkaline earth component oxide means MgO, CaO, BaO and SrO.
  • the above silicate glass is required to contain both the alkali component oxide and the alkaline earth component oxide. That is, the silicate glass contains at least one alkali component oxide selected from the group consisting of Li 2 O, Na 2 O and K 2 O and at least one alkaline earth component oxide selected from the group consisting of MgO, CaO, BaO and SrO, in a total content of at least 10 mol%.
  • the silicate glass may contain an oxide other than the above in order to obtain desired properties depending upon the purpose of use, as described hereinafter.
  • the present invention is applicable, in the case of glass for building and glass for automobiles, to glass having a composition comprising, as represented by mass percentage based on oxides, from 65 to 75% of SiO 2 , from 0 to 3% of Al 2 O 3 , from 5 to 15% of CaO, from 0 to 15% of MgO, from 10 to 20% of Na 2 O, from 0 to 3% of K 2 O, from 0 to 5% of Li 2 O, from 0 to 3% of Fe 2 O 3 , from 0 to 5% of TiO 2 , from 0 to 3% of CeO 2 , from 0 to 5% of BaO, from 0 to 5% of SrO, from 0 to 5% of B 2 O 3 , from 0 to 5% of ZnO, from 0 to 5% of ZrO 2 , from 0 to 3% of SnO 2 , from 0 to 0.1% of Se, from 0 to 0.1 % of CoO, and from 0 to 0.1% of Cr 2 O 3
  • the present invention is also applicable, in the case of glass for displays, to glass having a composition comprising, as represented by mass percentage based on oxides, from 50 to 72% of SiO 2 , from 0 to 15% of Al 2 O 3 , from 4 to 30% of MgO+CaO+SrO+BaO, from 0 to 10% of Na 2 O, from 1 to 20% of K 2 O, from 0 to 5% of Li 2 O, from 6 to 30% of Na 2 O+K 2 O+Li 2 O, and from 0 to 20% of ZrO 2 .
  • the present invention is also applicable, in the case of glass for hard disks, to glass having a composition comprising, as represented by mass percentage based on oxides, from 50 to 72% of SiO 2 , from 0 to 20% of B 2 O 3 , from 0 to 25% of Al 2 O 3 , from 0 to 30% of MgO+CaO+SrO+BaO, from 0 to 20% of Na 2 O, from 0 to 20% of K 2 O, from 0 to 20% of Li 2 O, from 6 to 30% of Na 2 O+K 2 O+Li 2 O, from 0 to 20% of ZrO 2 , from 0 to 20% of Y 2 O 3 , from 0 to 20% of La 2 O 3 and from 0 to 20% of ZnO.
  • a composition comprising, as represented by mass percentage based on oxides, from 50 to 72% of SiO 2 , from 0 to 20% of B 2 O 3 , from 0 to 25% of Al 2 O 3 , from 0 to 30% of MgO+Ca
  • the present invention is also applicable, in the case of chemically tempered glass for thin plates, to glass having a composition comprising, as represented by weight percentage based on oxides, from 50 to 75% of SiO 2 , from 0 to 20% of Al 2 O 3 , from 4 to 30% of MgO+CaO+SrO+BaO, from 0 to 20% of Na 2 O, from 0 to 15% of K 2 O, from 0 to 20% of Li 2 O, from 6 to 30% of Na 2 O+K 2 O+Li 2 O, and from 0 to 20% of ZrO 2 .
  • a composition comprising, as represented by weight percentage based on oxides, from 50 to 75% of SiO 2 , from 0 to 20% of Al 2 O 3 , from 4 to 30% of MgO+CaO+SrO+BaO, from 0 to 20% of Na 2 O, from 0 to 15% of K 2 O, from 0 to 20% of Li 2 O, from 6 to 30% of Na 2 O+K 2 O+Li 2
  • Each of the above glasses may contain As 2 O 3 , Sb 2 O 3 , MnO, NiO, V 2 O 5 , CuO or the like in an amount of at most 5% as additives.
  • the above glass may contain a colorant, for example, from 0 to 10% of Fe 2 O 3 , from 0 to 10% of TiO 2 , from 0 to 10% of CeO 2 , from 0 to 10% of CoO, from 0 to 10% of Cr 2 O 3 , from 0 to 1% of Se, or the like. More preferably the glass contains a colorant, for example, from 0 to 5% of Fe 2 O 3 , from 0 to 5% of TiO 2 , from 0 to 3% of CeO 2 , from 0 to 1% of CoO, from 0 to 1% of Cr 2 O 3 , from 0 to 1% of Se, or the like.
  • a colorant for example, from 0 to 10% of Fe 2 O 3 , from 0 to 10% of TiO 2 , from 0 to 10% of CeO 2 , from 0 to 10% of CoO, from 0 to 10% of Cr 2 O 3 , from 0 to 1% of Se, or the like.
  • the glass materials to be silicate glass to which the present invention is applicable contain a refining agent containing S (sulfur) element.
  • the S component as the refining agent may be contained in an amount of from 0.01 to 0.5% as calculated as SO 3 . If the addition amount of SO 3 exceeds 0.5%, the bubble layer in the melting tank 1 may be excessive. Further, if the addition amount of SO 3 is less than 0.01 %, the refining effect may be insufficient.
  • the present inventors have conducted studies on the vacuum-degassing method capable of suppressing formation of new bubbles by reboiling while effectively removing the bubbles in the molten glass. As a result, they have found that floating bubbles observed in the downstream region of the vacuum degassing vessel are the above-mentioned narrowly-defined reboil bubbles formed at the interface between the molten glass and the furnace material in the vacuum degassing vessel.
  • the origin of reboiling is SO 2 gas formed by decomposition of SO 3 contained in the molten glass under excessively reduced pressure, since the number of floating bubbles in the downstream region of the vacuum degassing vessel is influenced not only by the temperature and the degree of vacuum but also by the SO 3 concentration in the molten glass.
  • H 2 O gas formed from the moisture in the molten glass was also suspected.
  • the present inventors have found that even when the molten glass G supplied to the vacuum degassing vessel contains SO 3 at a concentration sufficient to obtain the refining effect, reboiling by SO 2 gas will not occur when the partial pressure of SO 2 gas formed by decomposition of SO 3 is lower than the pressure under which the SO 2 gas can be dissolved in the molten glass G, and accomplished the present invention which can effectively prevent reboiling.
  • Fig. 2 is a view illustrating the pO 2 values of molten glasses at 1,300°C of various silicate glasses, and chemical species of Fe and S dissolved in such molten glasses. It is evident from Fig.
  • pO 2 of the molten glass G at 1,300°C to be used in the vacuum-degassing method of the present invention is in a range of from 10 -4 to 10 -0.5 kPa indicated by oblique lines in Fig. 2 , and the state how S is present in the molten glass G is SO 4 2- ions.
  • the solubility of SO 4 2- in the molten glass is higher at a lower temperature, and higher when the pO 2 is higher and the glass is highly oxidizing.
  • the SO 4 2- concentration which can be dissolved in the molten glass G is determined by pSO 2 , pO 2 , the oxygen ion activity aO 2- and K (equilibrium constant) in the molten glass G.
  • the SO 4 2- solubility is higher.
  • aO 2- corresponds to the basicity of the glass determined by the glass mother composition.
  • SO 3 SO 3 as an oxide.
  • K' is the pseudo equilibrium constant including the influence of aO 2-
  • pSO 2 is the partial pressure (Pa) of SO 2 in the molten glass G
  • pO 2 is the partial pressure (Pa) of O 2 in the molten glass G
  • [SO 3 ] is the concentration (wt%) of SO 3 in the molten glass G.
  • pO 2 in the molten glass G is less than 10 -0.5 kPa, which is sufficiently lower than the absolute pressure in the vacuum degassing vessel 3.
  • pSO 2 can be determined. Since the SO 3 concentration change in the molten glass G as between before and after the molten glass G is passed through the vacuum degassing vessel 3 is negligibly small, [SO 3 ] can be known by fluorescent X-ray analysis of a plate-shape sample obtained by cooling the molten glass G after vacuum-degassed. Measurement of pO 2 in the molten glass G can be carried out by a commercially available oxygen sensor for molten glass employing zirconia electrolyte.
  • the pseudo equilibrium constant K' can be determined by measuring the SO 3 concentration in equilibrium with an atmosphere with known pSO 2 and pO 2 . The method for determining the pseudo equilibrium constant K' will be described hereinafter.
  • Fig. 8 is a graph illustrating the relation between the SO 2 supersaturation degrees SS (the second column from the right in Table 2) of SO 3 in the molten glasses G when various silicate glasses are vacuum-degassed and the frequency of reboiling (the rightmost column in Table 2).
  • at least the frequency of reboiling can be suppressed to be at most 10 bubbles/cm 2 /h.
  • at least the frequency of reboiling can be suppressed to be at most 2 bubbles/cm 2 /h.
  • no reboil bubbles will form in principle and as actual phenomenon.
  • the depth De (m) of the molten glass G flowing in the glass flow passage 3R of the vacuum degassing vessel 3 of the vacuum degassing apparatus 100 is set to satisfy the following formula (2): pS O 2 P G + ⁇ gDe ⁇ 2.0
  • pSO 2 is the partial pressure (Pa) of SO 2 in the molten glass
  • P G is the ambient pressure (Pa) of the vacuum degassing vessel
  • ⁇ is the specific gravity (kg/m 3 ) of the molten glass
  • g is the gravitational acceleration (m/s 2 ).
  • the molten glass G to be used in the vacuum-degassing method of the present invention may contain moisture.
  • the moisture contained in the molten glass G here means hydroxy groups represented by Si-OH.
  • the moisture in the molten glass G is derived from hydroxy groups in the materials, moisture adsorbed in the materials, water vapor contained in the atmosphere in which the glass is melted, and the like.
  • the moisture in the molten glass G functions as a component to refine glass by growing bubbles by formation of H 2 O gas in the vacuum-degassing step to increase the bubble floating speed and facilitate breakage of the bubbles.
  • the present inventors have conducted studies on the relation between the H 2 O supersaturation degree in the molten glass G and the frequency of formation of reboil bubbles.
  • Fig. 9 is a graph obtained by plotting the frequency of reboiling relative to the H 2 O supersaturation degree in the molten glass G, which will be described in detail in the after-mentioned Example 2. As evident from Fig. 9 , there was no correlation between the H 2 O supersaturation degree SH in the molten glass G and the frequency of formation of reboil bubbles.
  • the molten glass G should be passed in the glass flow passage 3R in the vacuum degassing vessel 3 under conditions satisfying the formula (1) and (2).
  • the vacuum housing 2 is evacuated of air by a vacuum degassing device (not shown) such as a vacuum pump from outside, whereby the vacuum degassing vessel 3 housed in the vacuum housing 2 is evacuated of air, and the interior of the vacuum degassing vessel 3 is in a reduced pressure state.
  • the average temperature of the molten glass G flowing in the glass flow passage 3R in the vacuum degassing vessel 3 is preferably from 1,050 to 1,350°C.
  • the viscosity of the molten glass G at a temperature of from 1,050 to 1,350°C is from 20 to 650 Pa ⁇ s.
  • the dimensions of the respective constituents for the vacuum degassing apparatus 100 may properly be selected as the case requires.
  • the dimensions of the vacuum degassing vessel 3 may be properly selected depending upon the vacuum degassing apparatus to be used, regardless of whether the vacuum degassing vessel 3 is made of platinum or a platinum alloy, or dense refractories. In the case of the vacuum degassing vessel 3 shown in Fig. 1 , the dimensions are specifically as follows.
  • the thickness is preferably from 0.5 to 4 mm.
  • the vacuum housing 2 is made of a metal, for example, stainless steel, and has a shape and dimensions capable of housing the vacuum degassing vessel 3.
  • the uprising pipe 5 and the downfalling pipe 6 may properly be selected depending upon the vacuum degassing apparatus to be used, regardless of whether they are made of platinum or a platinum alloy or dense refractories.
  • the dimensions of the uprising pipe 5 and the downfalling pipe 6 are as follows.
  • the thickness is preferably from 0.4 to 5 mm.
  • the vacuum degassing apparatus is not limited to the vacuum degassing apparatus 100 as shown in Fig. 1 , and modification is possible. Now, another general vacuum degassing apparatus will be described. In the following description, the same constituents as for the above-described vacuum degassing apparatus 100 are provided with the same symbols, and their explanations are omitted.
  • Fig. 3 is a cross sectional view schematically illustrating a general vacuum degassing apparatus.
  • a vacuum degassing apparatus 100B shown in Fig. 3 is different from the above-mentioned vacuum degassing apparatus 100 in that a glass flow passage 3R 2 in a vacuum degassing vessel 3B is set deep on the downstream side.
  • the vacuum degassing vessel 3B of the vacuum degassing apparatus 100B is formed so that a bottom wall 3a 2 (the bottom portion of the vacuum degassing vessel) of the vacuum degassing vessel 3B located on the downstream side of the glass flow passage 3R 2 is one step lower than a bottom wall 3a 1 of the vacuum degassing vessel 3B located on the upstream side of the glass flow passage 3R 2 , in order that the depth De of the molten glass G flowing on the downstream side of the glass flow passage 3R 2 satisfies the above formula (2).
  • a bottom wall 3a 2 the bottom portion of the vacuum degassing vessel
  • a step portion 3D as a boundary between the bottom wall 3a 1 and bottom wall 3a 2 is formed at a portion slightly closer to a downfalling pipe 6 than the middle of the uprising pipe 5 and the downfalling pipe 6, however, this is merely one example, and the position of the step portion 3D may be any position on the downstream side of the glass flow passage 3R 2 .
  • the depth h 1 on the upstream side of the glass flow passage 3R 2 is set shallower than the depth De on the downstream side.
  • the pressure at a bottom portion 3J 2 of the glass flow passage 3R 2 on the upstream side is lower than the pressure P abs at a bottom portion 3R b of the glass flow passage 3R 2 on the downstream side (that is, the degree of vacuum is higher) corresponding to a shallow depth of the molten glass G. Accordingly, in the molten glass G flowing in the glass flow passage 3R 2 on the upstream side, reboiling may occur.
  • the reboil bubbles will reach the surface layer of the molten glass G until the molten glass G flows to the downstream side, and the bubbles will be broken, whereby the molten glass can be degassed. That is, the upstream side of the vacuum degassing vessel 3B may be considered as a region where the sizes of all the bubbles including the reboil bubbles are positively enlarged, rather than suppressing reboiling.
  • the vacuum degassing apparatus 100B determines whether reboil bubbles form on the downstream side of the glass flow passage 3R 2 . If reboil bubbles form on the downstream side of the glass flow passage 3R 2 , the reboil bubbles are highly likely to be discharged from the downfalling pipe 6 without being broken, and bubbles may remain in molten glass and a glass product to be produced.
  • the depth of the molten glass is set so as to satisfy the formula (2) on the downstream side of the glass flow passage 3R 2 of the vacuum degassing vessel 3B, whereby reboiling on the downstream side of the glass flow passage 3R 2 can be suppressed. Therefore, according to the vacuum degassing apparatus 100B, remaining of bubbles in molten glass and a glass product to be produced can effectively be suppressed.
  • the region where the depth De of the molten glass G satisfies the formula (2) is set to a distance l 1 along a direction from the inner face end of a side wall 3b closest to the downfalling pipe 6 regarded as the downstream end of the glass flow passage 3R 2 toward the uprising pipe 5.
  • This distance l 1 is preferably L/2, wherein L is the full length of the glass flow passage 3R 2 of the vacuum degassing vessel 3B in a horizontal direction (that is, the full length of the vacuum degassing vessel 3B).
  • the distance l 1 may be shorter than L/2, and may properly be determined depending upon the reboil occurrence region.
  • the dimensions of the respective constituents for the vacuum degassing apparatus 100B may properly be selected, and for example, they can be set in the same manner as the above-described vacuum degassing apparatus 100.
  • the difference between the depth h 1 on the upstream side and the depth De on the downstream side of the molten glass G may properly be adjusted.
  • the depth De can be set deeper by about 1 m than the depth h 1 .
  • Fig. 4 is a cross sectional view schematically illustrating a general vacuum degassing apparatus.
  • a vacuum degassing apparatus 100C shown in Fig. 4 is different from the above-mentioned vacuum degassing apparatus 100 in that a slope 3K is formed on the downstream side of a glass flow passage 3R 3 of a vacuum degassing vessel 3C, and this slope 3K is set so that the depth of the molten glass G is gradually increased from the upstream side to the downstream side of the glass flow passage 3R 3 .
  • the vacuum degassing vessel 3C of the vacuum degassing apparatus 100C is formed, in the same manner as the vacuum degassing apparatus 100B, so that a bottom wall 3a 2 of the vacuum degassing vessel 3C located on the downstream side of the glass flow passage 3R 3 is one step lower than a bottom wall 3a 1 of the vacuum degassing vessel 3C located on the upstream side of the glass flow passage 3R 3 , in order that the depth De of the molten glass G flowing on the downstream side of the glass flow passage 3R 3 satisfies the formula (2).
  • the slope 3K as a boundary between the bottom wall 3a 1 and the bottom wall 3a 2 is formed at a position slightly closer to a downfalling pipe 6 than the middle of an uprising pipe 5 and the downfalling pipe 6, however, this is a mere example, and the position of formation of the slope 3K may be at any position on the downstream side of the glass flow passage 3R 3 .
  • vacuum-degassing can be carried out under conditions where the pressure P abs at a bottom portion 3R c on the downstream side of the glass flow passage 3R 3 satisfies the above formula (1), and reboiling can be suppressed.
  • the depth De of the molten glass G is set to satisfy the formula (2) within a range of a distance l 2 from the downstream end of the glass flow passage 3R 3 , whereby even if reboiling occurs in the molten glass G at the upstream side with a depth h 2 , reboil bubbles will reach the surface layer of the molten glass G and be broken until the molten glass G flows to the downstream side, whereby the molten glass can be degassed. Further, since the formula (2) is satisfied on the downstream side of the glass flow passage 3R 3 , reboiling on the downstream side of the glass flow passage 3R 3 can be suppressed. Therefore, according to the vacuum degassing apparatus 100C, remaining of bubbles in molten glass and a glass product to be produced can effectively be suppressed.
  • the slope 3K is continuously formed between a bottom portion 3J 3 on the upstream side with a depth h 2 of the glass flow passage 3R 3 and a bottom portions 3R c on the downstream side with a depth De of the glass flow passage 3R 3 .
  • the depth of the molten glass G flowing in a region where the slope 3K is formed is gradually increased from the depth h 2 to the depth De from the upstream side toward the downstream side. Accordingly, the flow rate of the molten glass G flowing in the slope 3K is gradually decreased along with an increase in the depth of the glass flow passage 3R 3 .
  • the floating speed of bubbles in the molten glass G can be increased relative to the flow rate of the molten glass G, whereby the vacuum degassing effect can be more increased.
  • the region where the depth De of the molten glass G satisfies the formula (2) is set to a distance l 2 along a direction from an inner face end of a side wall 3b closest to the downfalling pipe 6 regarded as the downstream end of the glass flow passage 3R 3 toward the uprising pipe 5.
  • the distance l 2 is preferably set within the same range as the distance l 1 of the vacuum degassing apparatus 100B as mentioned above.
  • the dimensions of the respective constituents for the vacuum degassing apparatus 100C may properly be selected, and for example, they can be set in the same manner as the above vacuum degassing apparatus 100.
  • the difference between the depth h 2 on the upstream side and the depth De on the downstream side of the molten glass G may properly be adjusted.
  • the depth De can be set deeper by about 1 m than the depth h 2 .
  • the angle of slope relative to the horizontal direction and the length in a horizontal direction of the slope 3K may properly be adjusted in accordance with the dimensions of the vacuum degassing apparatus.
  • a slope 3K having one smooth surface is exemplified.
  • the vacuum degassing apparatus is not limited thereto so long as retention of the molten glass in the vicinity of the upper edge of the downfalling pipe 6 can be suppressed.
  • the slope 3K may be stepwise, may be curved being concave down, or may be curved being concave up.
  • Fig. 5 is a cross sectional view schematically illustrating a general vacuum degassing apparatus.
  • a vacuum degassing apparatus 100D shown in Fig. 5 is the same as the vacuum degassing apparatus 100B in that a vacuum degassing vessel 3D is formed so that the depth of the molten glass is deeper on the downstream side of a glass flow passage 3R 4 , but is different from the vacuum degassing apparatus 100B in that a portion to reach a downfalling pipe 6D connected to the downstream side of the vacuum degassing vessel 3D is formed in a funnel shape, and the shape of a glass flow passage 6R therein is different from the vacuum degassing apparatus 100B.
  • a funnel-shape connection wall 6a 3 is formed at a boundary between a bottom wall 3a 1 of the vacuum degassing vessel 3D and a downfalling pipe 6D, and the depth De of molten glass G on the connection wall 6a 3 is set to satisfy the formula (2).
  • vacuum-degassing can be carried out under conditions where the pressure P abs of the molten glass G at a lowermost portion (bottom portion) 3R d on the downstream side of the glass flow passage 3R 4 , that is, located on the upper end portion of the connection wall 6a 3 satisfies the formula (1), and reboiling can be suppressed.
  • the depth De of the molten glass G is set to satisfy the formula (2) within a range of a distance l 3 from the downstream end of the glass flow passage 3R 4 , whereby even if reboiling occurs in the molten glass G on the upstream side with a depth h 3 , the reboil bubbles will reach the surface layer of the molten glass G and be broken until the molten glass G flows to the downstream side, whereby the molten glass can be degassed. Further, since the formula (2) is satisfied on the downstream side of the glass flow passage 3R 4 , reboiling itself on the downstream side of the glass flow passage 3R 4 can be suppressed. Therefore, according to the vacuum degassing apparatus 100D, remaining of bubbles in molten glass and a glass product to be produced can effectively be suppressed.
  • the glass flow passage 6R formed by the connection wall 6a 3 is formed as downwardly constricted, whereby the flow rate of the molten glass G flowing on the downstream side of the vacuum degassing vessel 3D and in the vicinity of the connection wall 6a 3 can be reduced, and the floating speed of the bubbles in the molten glass G can be made higher relative to the flow rate of the molten glass G, and the vacuum degassing effect can be more increased.
  • the region where the depth De of the molten glass G satisfies the formula (2) is set in a distance l 3 along a direction from an inner face end of a side wall 3b closest to the downfalling pipe 6D regarded as the downstream end of the glass flow passage 3R 4 toward the uprising pipe 5.
  • the distance l 3 is preferably set within the same range as the distance l 1 of the vacuum degassing apparatus 100B.
  • the dimensions of the respective constituents for the vacuum degassing apparatus 100D may properly be selected, and for example, they can be set in the same manner as the vacuum degassing apparatus 100.
  • the difference between the depth h 3 on the upstream side and the depth De on the downstream side of the molten glass G may properly be adjusted.
  • the depth De may be set deeper by about 1 m than the depth h 3 .
  • connection wall 6a 3 forming the downwardly constricted glass flow passage 6R above the downfalling pipe 6D is formed by a slope 6K 1 on the upstream side and a slope 6K 2 on the downstream side.
  • the angles of slope relative to the horizontal direction and the dimensions such as the length in a horizontal direction of the slopes 6K 1 and 6K 2 may properly be adjusted.
  • the vacuum degassing apparatus 100D shown in Fig. 5 an example is shown wherein the horizontal length of the slope 6K 1 on the upstream side is longer than the horizontal length of the slope 6K 2 on the downstream side.
  • the vacuum degassing apparatus is not limited thereto.
  • the angles of slope and the dimensions of the slopes 6K 1 and 6K 2 may be the same or different, and may properly be adjusted.
  • a general apparatus for producing molten glass is an apparatus comprising the above-described vacuum degassing apparatus 100 (or any one of 100B to 100D) and a melting device to melt glass materials to produce molten glass, disposed upstream the vacuum degassing apparatus 100.
  • the melting device is within the range of publicly known technique. For example, by the melting device, glass materials adjusted to have a desired composition are charged into a melting tank and heated to a predetermined temperature in accordance with the type of glass, for example, from about 1,400 to about 1,600°C in the case of silicate glass for building or for vehicles, to melt the glass materials thereby to obtain molten glass.
  • a general apparatus for producing a glass product is an apparatus comprising the above-described apparatus for producing molten glass, a forming device (forming apparatus) 200 to form the molten glass disposed downstream the apparatus for producing molten glass, and an annealing device to anneal the glass after formed.
  • the forming device and the annealing device are within the range of publicly known technique.
  • a forming device e.g. by a float process, a fusion method or a down draw method may be mentioned.
  • a forming device employing a float bath for a float process is preferred from a reason such that mass production of high quality plate glass in a wide range of thickness from thin plate glass to thick plate glass is possible.
  • an annealing device an annealing furnace equipped with a mechanism to gradually lower the temperature of the glass after formed is commonly employed. By the mechanism to gradually lower the temperature, heat, the output power of which is controlled by combustion gas or an electric heater, is supplied to a necessary position in a furnace to anneal glass after formed, whereby residual stress in glass after formed can be eliminated.
  • Fig. 6 is a flow chart illustrating an embodiment of the process for producing molten glass of the present invention.
  • the process for producing molten glass of the present invention comprises the method for vacuum-degassing molten glass of the present invention.
  • it is a process for producing molten glass, which comprises a melting step S1 of melting glass materials by the melting device at a stage prior to the vacuum degassing apparatus 100 to produce molten glass, a degassing step S2 of degassing molten glass by the above-described method for vacuum degassing molten glass, to obtain molten glass G3.
  • the process for producing molten glass of the present invention is within the range of publicly known technique except that the above-described method for vacuum-degassing molten glass is employed. Further, the apparatus utilized in the process for producing a glass product of the present invention is as described above.
  • FIG. 7 is a flow chart illustrating an embodiment of the process for producing a glass product of the present invention.
  • the process for producing a glass product of the present invention is characterized by employing the above-described process for producing molten glass.
  • the process for producing a glass product of the present invention comprises a step K1 for producing molten glass by the above-described process for producing molten glass, a forming step K2 of forming the molten glass downstream the step K1 for producing molten glass, and an annealing step K3 of annealing the molten glass in a subsequent step, to obtain a glass product G5.
  • the process may have a cutting step of cutting the glass after annealed and/or other subsequent steps K4.
  • the process for producing a glass product of the present invention is within the range of publicly known technique except that the above-described process for producing molten glass is used. Further, the apparatus employed in the process for producing a glass product of the present invention is as described above. In Fig. 7 , in addition to the melting step, the forming step and the annealing step as constituents for the process for producing a glass product of the present invention, a cutting step and another subsequent step carried out as the case requires are also shown.
  • each of glasses as identified in Tables 1 and 2 was melted in a platinum crucible, and the resulting molten glass was transferred into a crucible made of alumina electrocast refractories (manufactured by AGC CERAMICS CO., LTD., "MB-G", tradename, Al 2 O 3 : 95 to 96 mass%, Na 2 O 3 : 3 mass%, slight amounts of SiO 2 and CaO contained) via a platinum passage, and the crucible made of alumina electrocast refractories in which the molten glass was put was disposed in a melting vacuum container.
  • alumina electrocast refractories manufactured by AGC CERAMICS CO., LTD., "MB-G", tradename, Al 2 O 3 : 95 to 96 mass%, Na 2 O 3 : 3 mass%, slight amounts of SiO 2 and CaO contained
  • the respective components for the glass in Table 1 are represented by wt%, and values in brackets are represented by mol%.
  • the atmosphere including the crucible made of alumina electrocast refractories was heated to further melt the glass, and the temperature of the molten glass was adjusted to the temperature shown in Table 2. Then, under the absolute pressure of the molten glass at the bottom portion in the vacuum container being the pressure P abs (kPa) as shown in Table 2, vacuum-degassing treatment was carried out.
  • Bubbles floating from the molten glass in such a state were imaged by a CCD camera through an observation hole provided on the upper portion of the crucible made of alumina electrocast refractories, and the number of bubbles having diameters of 0.5 mm or larger were measured to determine the frequency of reboiling (bubbles/cm 2 /h) of the molten glass.
  • the degree of vacuum was maintained by melting in the crucible made of alumina electrocast refractories.
  • observation of the bubbles was conducted after a lapse of 3 days from initiation of melting. This is because bubbles regardless of the test conditions form from the furnace material at the initial stage of the test.
  • the results are shown in Table 2.
  • the glasses A1 to A8 shown in the column of glass type in Table 2 are glass A in Table 1
  • glasses B1 to B6 are glass B in Table 1
  • glasses C1 to C6 are glass C in Table 1
  • glasses D1 to D6 are glass D in Table 1.
  • Fig. 8 the relation between the SO 2 supersaturation degrees SS of the respective molten glasses and the frequency of reboiling is shown.
  • Measurement of the SO 3 concentration [SO 3 ] was carried out by a fluorescent X-ray analyzer using a sample obtained by pulverizing a plate-shape sample obtained by cooling the molten glass.
  • pO 2 in the molten glass was measured by re-melting the plate-shape sample obtained by cooling the molten glass in an experimental furnace.
  • the experimental furnace used for measurement was pO 2 measuring apparatus Rapidox (manufactured by Heraeus Electro-Nite). The measurement procedure is as follows. Seven hundred grams of a plate-shape sample was put in a dedicated crucible made of sintered quartz and re-melted at 1,400°C.
  • the temperature was lowered to 1,300°C, and an oxygen sensor probe (reference material Ni/NiO) employing zirconia solid electrolyte was inserted into the matrix, and measuring was carried out sequentially lowering the temperature to 1,250°C and 1,200°C.
  • the crucible was rotated at 4 rpm.
  • the pseudo equilibrium constant K' a value calculated from the formula (11) determined by the following method was employed.
  • the pseudo equilibrium constant K' can be strictly evaluated as a function of the temperature by measuring the SO 3 concentration in equilibrium with known pSO 2 and pO 2 at the respective temperatures.
  • glass having a model composition comprising 71.5 mass% of SiO 2 , 1.5 mass% of Al 2 O 3 , 13.5 mass% of Na 2 O, 0.5 mass% of K 2 O, 4.5 mass% of MgO and 8.5 mass% of CaO, which is a simulation of the molten glass to be used for the vacuum degassing method of the present invention, was employed.
  • the absolute pressure P abs of the molten glass at the bottom portion of the crucible was adjusted to the value as shown in Table 3, and bubbles in the molten glass were imaged by a CCD camera from an observation hole provided on the vacuum degassing apparatus, and the number of bubbles having diameters of 0.5 mm or longer were measured to determine the frequency of reboiling (bubbles/cm 2 /h).
  • the results are shown in Table 3 and Fig. 9 .
  • the glasses A1 to A8 shown in the column of glass type in Table 3 are glass A in Table 1.
  • K w is a value determined based on the moisture solubility data of conventional soda lime glass as disclosed in a literature ( High Temperature Glass Melt Property Database for Process Modeling, Edited by T. P. Seward III and T. Vascott, Wiley-American Ceramic Society ), and values of 2.70 ⁇ 10 5 at 1,300°C and 2.66 ⁇ 10 5 at 1,200°C were employed.
  • Fig. 9 is a graph obtained by plotting the H 2 O supersaturation degree SH in the molten glass and the frequency of reboiling. As described above, no correlation between the H 2 O supersaturation degree SH in the molten glass and the frequency of reboil bubbles, as between the SO 2 supersaturation degree SS and the frequency of reboiling, was confirmed.
  • Example 2 The same test as in Example 1 was carried out with respect to glass composition B in Table 1 except that the crucible made of alumina electrocast refractories into which the molten glass was put at the time of the vacuum-degassing treatment was changed to a crucible made of platinum.
  • the results are shown in Table 4. From the results, it was found that reboil bubbles are less likely to form in a case where the crucible into which the molten glass was put was made of platinum, as compared with the case of the alumina electrocast refractories. Further, it was found that in a case where the crucible into which the molten glass was put was made of platinum, molten glass with good bubble quality can be produced by adjusting the SO 2 supersaturation degree SS to about 4.3.
  • the glasses B7 and B8 shown in the column of glass type in Table 4 are glass B in Table 1.
  • TABLE 4 Glass type Molten glass temperature (°C) P abs (kPa) [SO 3 ] (wt%) log ⁇ O 2 (kPa) pSO 2 (kPa) SO 2 supersaturation degree SS Frequency of reboiling (bubbles/cm 2 /h) B7 1,300 17.3 0.148 -0.96 36.7 2.1 0.0 B8 1,220 8.0 0.043 -3.14 34.4 4.3 0.0
  • the method for vacuum-degassing molten glass, the process for producing molten glass, and the process for producing a glass product of the present invention are applicable to production of a variety of glass products for building, for vehicles, for optical use, for medical use and for other uses.

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Claims (5)

  1. Procédé de dégazage sous vide de verre fondu, qui comprend la fusion de matériaux de verre devant devenir du verre silicaté et le passage du verre fondu résultant dans un passage d'écoulement dans un récipient de dégazage sous vide, dont l'intérieur est maintenu sous pression réduite, pour dégazer sous vide le verre fondu,
    dans lequel les matériaux de verre devant devenir du verre silicaté contiennent un agent de raffinage contenant du S (soufre) élémentaire,
    dans lequel le dégazage sous vide du verre fondu est effectué dans des conditions satisfaisant aux formules (1) = (2) et (7) qui suivent au moins au niveau d'une partie de fond du côté aval du passage d'écoulement de verre du récipient de dégazage sous vide : SS = pSO 2 / P abs = pSO 2 / P G + ρgDe < 2,0
    Figure imgb0020
     pS O 2 = K t × S O 3 p O 2
    Figure imgb0021
     où, dans la formule (1) = (2), SS est le degré de sursaturation du SO2 dans le verre fondu, pSO2 est la pression partielle (Pa) du SO2 dans le verre fondu, Pabs est la pression (Pa) au niveau de la partie de fond du passage d'écoulement de verre du récipient de dégazage sous vide, PG est la pression ambiante (Pa) dans le récipient de dégazage sous vide, p est le poids spécifique (kg/m3) du verre fondu, g est l'accélération gravitationnelle (m/s2), et De est la profondeur (m) du verre fondu s'écoulant sur la côté aval d'un passage d'écoulement de gaz du récipient de dégazage sous vide, et, dans la formule (7), pSO2 est la pression partielle (Pa) du SO2 dans le verre fondu, Kt est la pseudo-constante d'équilibre comprenant l'influence d'O2-, [SO3] est la concentration (% en poids) du SO3 dans le verre fondu, et pO2 est la pression partielle (Pa) de l'O2 dans le verre fondu.
  2. Procédé de dégazage sous vide de verre fondu selon la revendication 1, dans lequel le verre silicaté a une composition de SiO2 ≥ 50 % en moles et (oxyde de composant alcalin plus oxyde de composant alcalino-terreux) ≥ 10 % en moles.
  3. Procédé de dégazage sous vide de verre fondu selon la revendication 1 ou 2, dans lequel le dégazage sous vide est effectué dans des conditions satisfaisant à la formule (1)=(2) ci-dessus dans la plage allant de l'extrémité aval du passage d'écoulement de verre à L/2, où L est la pleine longueur du passage d'écoulement de verre du récipient de dégazage sous vide dans la direction horizontale.
  4. Procédé pour produire du verre fondu, qui comprend une étape de dégazage de verre fondu par le procédé de dégazage sous vide de verre fondu tel que défini dans l'une quelconque des revendications 1 à 3, et une étape de fusion des matériaux du verre fondu avant l'étape de dégazage.
  5. Procédé pour produire un produit en verre, qui comprend une étape de production de verre fondu par le procédé pour produire du verre fondu tel que défini dans la revendication 4, une étape de formation consistant à former le verre fondu en aval de l'étape de production de verre fondu, et une étape de recuit consistant à recuire le verre après formation.
EP12770966.5A 2011-04-12 2012-04-09 Procédé de dégazage sous vide de verre fondu, procédé de fabrication de verre fondu, procédé de fabrication d'un article constitué de verre Active EP2698354B1 (fr)

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BR112013025911A2 (pt) 2016-12-20
JP5975022B2 (ja) 2016-08-23
CN103476715B (zh) 2015-12-23
EP2698354A4 (fr) 2014-12-17
KR20140010940A (ko) 2014-01-27
CN103476715A (zh) 2013-12-25
JPWO2012141152A1 (ja) 2014-07-28
EP2698354A1 (fr) 2014-02-19

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